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Q.(a) Explain hydrate (solvate) isomerism and linkage isomerism with suitable examples.

(b) Explain the use of radioactive isotopes in the study of mechanism of photosynthesis in plants and hydrolysis of esters.
Tamil Nadu DgeTamil Nadu HSC (DGE) Board 2018Subjective· 10mImportance★★★★★
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(a) Hydrate isomerism arises from water being either a coordinated ligand or lattice water; linkage isomerism arises from an ambidentate ligand binding through either of its two donor atoms. (b) 18O^{18}O-labelled water traces the origin of photosynthetic oxygen (from water) and the site of bond cleavage in ester hydrolysis (the acyl–oxygen bond).

(a) Hydrate (solvate) isomerism

This type of isomerism arises among hydrated coordination compounds when water molecules can be distributed differently between (i) the coordination sphere, where they act as ligands directly bonded to the metal, and (ii) the crystal lattice, where they exist as "water of crystallisation" and are not bonded to the metal. Because the total formula (e.g. CrCl3⋅6H2OCrCl_3 \cdot 6H_2O) is the same in every isomer, but the number of ligands actually coordinated differs, the isomers differ in colour, conductivity (number of free ions), and reactivity.

Classic example — CrCl3⋅6H2OCrCl_3 \cdot 6H_2O has three known hydrate isomers:

  • [Cr(H2O)6]Cl3[Cr(H_2O)_6]Cl_3 — violet; all 3 Cl−Cl^- ions are free (ionisable), giving the highest conductivity.
  • [Cr(H2O)5Cl]Cl2⋅H2O[Cr(H_2O)_5Cl]Cl_2 \cdot H_2O — grey-green; 2 free Cl−Cl^- ions, 1 lattice water; intermediate conductivity.
  • [Cr(H2O)4Cl2]Cl⋅2H2O[Cr(H_2O)_4Cl_2]Cl \cdot 2H_2O — dark green; only 1 free Cl−Cl^- ion, 2 lattice waters; lowest conductivity.

These can be distinguished experimentally by titrating a solution against AgNO3AgNO_3: the number of Cl−Cl^- ions precipitated as AgClAgCl immediately corresponds to the number of free (ionic) chloride ions, not the total chlorine content.

Linkage isomerism

This arises when the complex contains an ambidentate ligand — a ligand possessing two different atoms, either of which can act as the donor atom to the metal. Depending on which atom binds the metal, different (linkage) isomers result.

Common ambidentate ligands: −NO2−-NO_2^- (can bind through N as "nitro" or through O as "nitrito"), −SCN−-SCN^- (can bind through S as "thiocyanato" or through N as "isothiocyanato").

Example:

  • [Co(NH3)5(NO2)]Cl2[Co(NH_3)_5(NO_2)]Cl_2 — pentaamminenitrito-N-cobalt(III) chloride (nitro form, Co–N bond), yellow-brown, stable.
  • [Co(NH3)5(ONO)]Cl2[Co(NH_3)_5(ONO)]Cl_2 — pentaamminenitrito-O-cobalt(III) chloride (nitrito form, Co–O bond), red, less stable, isomerises to the nitro form on standing/heating.

(b) Radioactive (isotopic) tracer studies

Mechanism of photosynthesis: The overall photosynthesis equation is 6CO2+6H2O→lightC6H12O6+6O26CO_2 + 6H_2O \xrightarrow{\text{light}} C_6H_{12}O_6 + 6O_2, but it was originally unclear whether the evolved oxygen came from CO2CO_2 or from H2OH_2O. In the classic tracer experiment (Ruben and Kamen), plants were supplied with water enriched in the heavy isotope 18O^{18}O (i.e. H218OH_2{}^{18}O) together with ordinary (unlabelled) CO2CO_2. The O2O_2 gas evolved by the plant was found to be enriched in 18O^{18}O, matching the label in the water, not in the CO2CO_2. This proved that the oxygen liberated in photosynthesis originates entirely from the photolysis (splitting) of water, and not from carbon dioxide:

6CO2+12H218O→light, chlorophyllC6H12O6+6 18O2+6H2O6CO_2 + 12H_2{}^{18}O \xrightarrow{\text{light, chlorophyll}} C_6H_{12}O_6 + 6\,{}^{18}O_2 + 6H_2O

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